Process of making stannic chlorid.



- No. 810,454. j l PA'IE1\ITBD.JAN` 23,'.l9 06.

'.G.l E. AGKER.- PROCESS QF MAKING ASIAIIIIIG GHLORIDLl urmcnxon runnin; a '1903. Mmmm JUNE 15,1905.

UNrrED STATES PATENT- OFFICE.

CHARLES E. ACKER, OF NIAGARA FALLS, NEW YORK, ASSIGNOR TO ACKER PROCESS COMPANY, A CORPORATION OF NEW` JERSEY.

ipeccaton of Letters IPatent.l

v Patented Jan. 28, 1906.

Applicatiiin led June 8, 1903. Renewed June 14, 1905. Serial No. 265,237. v

To (LN, whom, it may concern:

, Be it known that I, CHARLES E. ACKER, a 'eitizenof the United States, residing at Ni- .\agara Falls, in the county of Niagara and State .of New York, have invented certain new and useful Improvements in Methods of Making Stannic' Chlorid, of which the following is a speciiication., y This invention is a method of making stannic chlorid, whereby it is possible to .obtain solutions of a concentration heretofore 'unknown as' a commercial product and of a high degree of purity. Heretofore it has been customary to'prepare solutions of this. sort by reacting upon metallic tin with hydrochloric acid in solution, thereby forming stannous chlorid, andsubsequently converting said chlorid to stannic chlorid by addition of potassium chlorate to the acid solution. This process is relatively expensive, since the chlorin is derived from the comparatively costlycompounds, hydrochloric acid and -potassium chlorate, .and is furthermore subjectgto the disadvantages that'thefsolutions produced cannot, in practice exceed aA density of to 51 Baume, andare contaminated by the presence of considerable uantities of potassium chlorid derived from t e reduction of the chlorate. Furthermore, it' is impractical to concentrate such solutions, by reason of the loss of stannicl chlorid by volatilization and the tendency of the solutions to become basic. Solutions of a density Aof o Baume have been prepared by first produc-ings; solution of stannous chlorid, concentrating the same to saturation, and subsequently converting it.by means of potassium chlorate to stannicchlorid; but this process is an expensive'one, and the solutions obtained are also contaminated by potassium chlorid. I have now discovered a simple and effective method of producing stan-' nic-chlorid solutions of extremely high con centration, the specific gravity of which may vary from 1.800 to 1.9600, which solutions are \juncontaminated .by impurities of any kind, According to my method chlorin is employed in a free or uncombined state, and theprocess admits, therefore, of a high degreegof economy;I I

-Feria full understanding of my'invention referepceile made to the accompanying drawings, wherein- Figdre 1 show-s vin vertical section one form of apparatus which may be used forcarrying out my process., Fig. 2 is a similar view showing a modified form thereof. Fig. 3 is a s imilar view of a further modiication.

Referring to Fig. 1, 1 represents a vat or -tank which may conveniently be of .glazed earthenware. 2 is a storage-reservoir, and 3 a reaction-tower, shown as of the Rohrmann type, but which may be of any desired character. Means consistin of a conduit 4 and an air-injection ipe 5, leading into the lower portion thereo are provided for continuously or intermittently conveying the solution in the tank 1 to the storage-reservoir 2. From said reservoir the li uid is permitted to flow downwardly throug tower 3 and to return thence by conduit 6 to the vat 1. The vat 1 contains, in addition to the liquid to behereinaiter described, a mass of 'metallic tin, preferably in a suitably-divided condition, and to maintain a body of clear liquid in the region of the inlet to the conduit 4 said conduit 1s surrounded by a protective casing 7, which is conveniently provided with apertures 8 .at the lower end for the admission of the liquid.

process depends upon the fact that certain tin salts, vinwhich the tin is in the tetravalent state, are extremelyenergetic solventsv for metallic tin, the metal passing into solution and the tin in the solvent liquid being reduced in whole or in part to thedivalent state. The liquid havinor thus lost a part or all of its lsolvent power fior tin is thereupon brought into contact with chlorin gas under the conditions to be hereinafter described, whereby it is a ain raised wholly or in part Jto the tetrava ent condition, with corresponding restoration o f its solvent power. This regenerated solvent is again brought into contact with metallic tin and again regenerated, the operation proceeding in this "manner until any required 'concentration is reached, whereupon the stannic-chlorid soluy tion is withdrawn from the system, for instance, through lthe cock 9 and is utilized as desired, an equivalent amount of water or of Water containing stannic or stannous chlorid or hydrochloric acid being added, and 'the' process. continued as before. If desired', the process may be made continuous bythe gradual Withdrawal of the stannic-chlorid solution and the addition. of corresponding uantities of water or chlorid solutions. To o tain the IOO solution containing the tin-in the tetravalent condition, itI may be withdrawn from the system at a point immediately following the treatment with chlorid. If the liquid contains an excess of chlorin, said excess is removed by the careful addition of stannous chlorid and a clear, pure, colorless, and dense solution is obtained.

Fig. 2 shows a modified form of device, ii which the liquid after being subjected to the ,action of chlorin in the reaction-tower 3 is permitted to iiow into one of a series of pressure-tanks 1, a number of such tanks being provided, and filled and discharged in succession, as will be readily understood. Said tanks l contain metallic tin, and after the solvent has been permitted to remain in con.

tact therewith for a sufficient time thc tank is closed and air-pressure applied above the 2O surface of the liquid by means of a pipe 5', the liquid being thereby forced to the upper reservoir 2, Vfrom which it returns throlugh the tower 3, as above described. It will be obvious that any suitable means for securing the cir- 23 culation of the liquid may be substituted for those described.

ln F 3 I have shown a further modification, wherein an .intermediate tank, tower, or vat l() is provided to contain the metallic tin and permit the reaction therewith of the solventI liquid from the tower. In said tank 10 l have shown a distributing-platc l1 for the inflowingl solution and a discharge-pipe 13 for the delivery of the same to the pres- 3 5 sure-tank or other elevating device 1.

These several devices for carrying out my method are shown by way of illustration only, and l. desire it to be understood that my method is not limited to the employment of any particular apparatus. l have shown at 14 i5 an inlet and outlet,

` respectively', for the gas which serves to convert the tin from its divalent to its tetravalent condition and have referred to this gas as chlorii'r7 l have discovered,however, that it is neither necessary nor advisable to use pure chlorin gas for this purpose, but that the gas may contain a large proportion of an' or oxygen. o reaction is facilitated by the injectionof steam into the chlorin, as by pipe 16, with the consequent formation of hydrochloric acid or by the use of chlorin containing a certain proportion of hydrochloric acid.

l. have employed a gaseous mixture containing ninety-'live to ninetysix per cent. of air, four--toflive per cent. chlorin, and a small percentage of hydrochloric acid. It will be understood that the reaction evolves a cen- 6 o siderable amount of heat and that the temperature, if uncontrolled, would rise rapidly to a. point at which l'iydrochloric acid and stannic chlorid would be volatilized, metastannates formed, and the solution injuriously affected. The usc of dilute chlorin, as del have further discovered that the` scribed, possesses the advantage that a por tion of this heat is absorbed in raising the temperature of the large volume of gas so provided, and that therefore it is possible to utilize larger absolute quantities of chlorin in a given time that is to say, one result of employing a dilute gas is to materially increase the output from a given apparatus. The addition of hydrochloric acid to the gas or to the solution or the utilization of gases con- `taining hydrochloric acid results in the acceleration of the solvent action of stannic chlorid upon metallic tin and serves also to prevent the formation of oxychlorids of tin, the presence 'of which is in general undesirable.

It will be understood that the dilution of the chlorin need not be so great as above indicated by way of example and that .proportionate effects are secured by the use of smaller proportions of the diluent.

It will be obvious that the character of the original liquid, which under the conditions of my process is to become a solution of stannic chlorid, may be considerably varied. Thus water may be employed or any desired proportion of stannic chlorid, stannous chlorid, hydrochloric acid, or stannous or stannic oxychlorid maycbe added thereto. In an): case the result of the treatment by chlorin is to form a solvent for tin, and the result of the repeated utilization and regeneration of this solvent is to form solutions of stannic chlorid of'al concentration heretofore unattainable in a commercial way.

The reaction proceeds with greatest facility at a temperature of 5()o to 60O centigrade; but the process may be carried out at any temperature below the point at which stannic chlorid is volatilized.

I claim- '1. The method of making stannic chlorid, which consists in bringing metallic tin into contact With a solvent containing chlorin, thereby producing a solution containing stannous chlorid, and subjecting said solution to the action of a gaseous mixture containing in su'liicient proportion to prevent unduerise of temperature, substantially as described.

'2. The method of making stannic chlorid which consists in bringing lmetallic tin into contact with a solvent containing chlorin, thereby producing a solution containing stannous chlorid, and subjecting said solution to the action oi' a gaseousanixture containing free chlorin, hydrochloric acid and a diluent., the diluent being in sufficient proportion to tially as described.

The method of making stannic chlorid which consists in bringing metallic tin into contact with a solvent containing chlorin, thereby producing a solution containing stannous chlorid, and subjecting said solution to IIO free chlorin and a diluent7 the diluent being c prevent undue rise of temperature, substan until tne ueslred concentration is'reacned Eil-93% ilsolntion to the action oi" free chlo'rin to con@ vert it into stannic chiorid, bringing said l stannii' chlorid to contact with further guar 'vi-'ies of tin, and converting i, sta-uuic chloridJ and. repeating the 'operation until tse desired concentration is reached,

` -antially as des ed The method ot in J 1`iglilyconcen trated solutions containing stannic clilorid which consists in l `inging metallic tin into contact with a solvent containing cl'ilorin, thereby producing o solution of stannous rid, subjecti..LA d solution to the action ciilorinto c ert it into stannic ohio-- rid, bringing soir. nic chlo 1 to contact with furti -zi'uontmies of tin, again converting it -no stannic clilcrid, and repeating the operation until the concentration exceeds i KOU specific gravity, substantial-ly as de scribed.

6. The method of making solutions containing stannic chlorid which consists in bringing metallic tin into contact with a solvent containing chlorin, thereby producing e solution of stannous chloriol7 subjecting said soiution to the action of a gaseous mixture containing free oblorin and hydrochloric acid to convert it finto stannic clfilorid, bringin said stannic chlorid into contact with lurtiie quantities of tinI and again converting it intr stannic chlorid, ond repeatmg the operati `n "i HUD substantiallIv as described.

7. The method of making solutions containing stannic chlorid wl h consists in bringing metallic tin into co. with a solvent containing chlorin, thereby producing a solution of stannous chlorid, subjecting said solution to tbe action of a. g eous inizi-ture containing free chlorin hydrochloric acid and oxygen convert it into stannic clilorid, bringing said stannic chlorid into Contact with further quantities of tin, and again con.- rerting it into stannic clilorid, ind repeating the operation until the desired concentration i. reached, substantially as described.

The method of making solutions containing stannic chlorid which consists in bringing metallic tin into contactwitli a solvent contaiiung chlorin, thereby produc-i" g a, solution oistannous chloridl` subjcctin(y said solution to the action of ay gaseous xturc containing free chlorin, hydrochloric acid :3nd atrniisnlierio air to convert it into stannic A wliicii consists clilorid, bringing said stannic clilorid into 'i contact Witii further quindi-es oi tin, and again converting it into stannio chlorro', and

repeating operation untii the desired concentration reached, substantially as described.

9. miie iicieirndescribed method oi limiting stannic chlorid, which consists in subjecting a ution containing s"'innous chlorid to the prevent undue rise ci tei iperature, substantiall-v is described.

l0. The herein-described n"thod of nialin ing stannic chlorid, which cosists in subjecting a sol tion containing stannous clxlorid to t'e action oi a gaseous mixture containing cliloriif, hydrochloric scid and a dilucnt7 the diluent being in sui'licient p 'iortion to prevent undue risc et ten'ijjiereture, substantiallyv is described,

il. herein-described inethod oi inaliing stsnnic chlorid, which consists in subjecting e solution containing stannous chlorid to tbe action of gaseous mixture containing free chlorin7 hydrochloric acid and atmospheric air, substantialiy es described.

l2. The inotliod oi making stannic clilorid, in subjecting a solution conu taining stannous chlorid to tbe action o1" a liuid. containing free clilorin, thereby producing a solution containing stannic chloid, bringing said stannic-chlorid solution into contact with metallic tin to form stanncus clilorid and :subjecting stannous-cblorid solution to the action of a iuid containing free chlorin, substantialiy as described.

13. The method ot making stannic chlorid which consists in subjecting a soiution con? taining stannons chlorid to the action of :i fluid containing free chlorini tberebj.T produca solution containing stannic cblorid, bringing seid stannic-chlorid solution into contact with metallic tin to torni stsnnous chlorid, subjecting said stannouschiorid soiution to the action of o .fluid containing free cbiorin, repeating the operation until the desired concentration is reached, substantially as described 14. The method ci making stannic chlorid, which coi :ists in subjecting a soiution containing es'annous cblorid to the action of ay uid con Nining free chlorin, thereby producing e solution containing stannic chiot-id, bringing said stanniochlorid solution into contact with metallic tin to forrn stannous chlorid, subjecting said stannous-clilvorid solution to the action of a i'iuid containing free' chlorinJ and repeating the operstion until tli concentration exceeds t8 specific gravity, substantially as described.

15. The inet-nod making stannic chlorif, wl ich consists in subiecti g a solution cong iic clilorid to the action of metal-- lic tin; tlierfl iorn'iing stannous chiorid, and subjecting said stannousclilorid solution to IOC IIO

the action of ay Vfluid containing free chlolin to produce a. solution containing enlincreascd amount of stannic chlorid, substantially as described.

16. The herein-described method of producing solutions containing stennic chlorid, which consists in subjecting n. solution capable of dissolvingnti'n as chloiid to the successiveection of metallic tin and a Huid contain- Io ingr 'ee chlofin, substantially as described.

- l?. The herein-described method of producing solutions containing chlorid of tin, which consists in subjecting a solution containing a compound of chlorin to the alternate action of metallic tin and a Huid containing free chlorin, substantially as described.

In testimony whereof I a'lix my signature in presence of two witnesses.

CHARLES E. ACKER. Witnesses:

J. H. SCHENNERHORN, D. S. MACK/n'. 

